NZ502406A

NZ502406A - Bio-soluble glass fiber composition that has a minimised residence time in lung, decreasing the subsequent lung associated disease

Info

Publication number: NZ502406A
Application number: NZ502406A
Authority: NZ
Inventors: Charles F Rapp; Stephanie M Mattson
Original assignee: Owens Corning Fiberglass Corp
Priority date: 1997-08-04
Filing date: 1998-07-29
Publication date: 2001-06-29
Also published as: AU8668698A; US6034014A; WO1999006332A1; EP1027298A4; CA2296408A1; EP1027298A1; AU735688B2

Abstract

A glass composition containing at least 2.0 wt % Al2O3 to give resulting glass fiber an acceptable chemical durability for product performance, but no more than 3.0 wt % to ensure the fiber maintains a relatively high bio-solubility. The composition further includes relatively high amounts of Na2O+K2O+MgO+CaO, that tends to increase fiber bio-solubility and allows for the use of reduced amounts of B2O3 in the composition. The glass compositions have KI values that generally equal or exceed a KI value of 40 and are suitable for rotary processing. The compositions have liquidus temperatures TL (oF) below 1800oF and viscosities above 300 Poise at the liquidus temperature. For higher B2O3 compositions the liquidus temperatures are below 1650oF, and the viscosities are above 1,000 Poises at the liquidus temperatures.

Description

GLASS FIBER COMPOSITION The present invention is directed generally to glass compositions, and more particularly to glass fiber compositions having high KI values and structural durability.

Glass fiber, or fiberglass, insulation is well known and has been a commercial product for many years. Glass fiber insulation is widely used both residentially and commercially.

Generally, the insulation is made from intertwined soda lime alumina borosilicate glass fibers which are held together with a binder. The glass fibers are generally produced 10 using Si02 with a number of additives, such as Na20, K20, CaO, MgO, BaO, B203, and AljOj, that enhance various properties of fibers. The binder may be any suitable material, but quite commonly is a phenol-formaldehyde resin or a urea formaldehyde resin.

A rotary process is often used to form the glass fibers. The rotary process typically involves the introduction of molten glass into a rotating device, called a spinner, which 15 contains a plurality of holes circumferentially distributed around the spinner. The spinner is rotated about an axis to produce a centrifugal force on the molten glass. The rotation of the spinner forces the molten glass through the plurality of holes.

An annular stream of hot gases is passed around the spinner to contact and attenuate the fibers passing through the holes. A spray nozzle is positioned to coat the 2 0 attenuated fibers with the binder.

A conveyer collects the binder-coated fibers in the form of a blanket, or batt, and the blanket is heat cured to produce the final insulation. The rotary process can be used to produce insulation having different densities by varying the conveyer speed and the thickness of the cured insulation.

Glass fiber insulation has been used to replace, or in lieu of, asbestos fiber insulation in many applications. It is generally believed that asbestos fibers, when inhaled, can result in significant disease in man. Though the exact mechanism responsible for the biological activity of asbestos fibers is unknown, it is widely believed that an important factor in the mechanism is the residence time of the fibers in the lungs. 30 Unlike asbestos fibers, glass fibers have not been linked to disease in man. Glass fiber also appears to have a much shorter residence time in the lungs than asbestos fibers.

The residence time of glass fibers in the lungs will depend, at least in part, upon chemical dissolution of the fiber. The rate of chemical dissolution of a material in 1 Printed from Mimosa WO 99/06332 PCT/US98/1S701 biological fluid is generally referred to as the biosolubility or biological degradability of the material.

Despite the lack of a link between glass fibers and human disease, some countries, for example Germany, have proposed regulations for the use of glass fibers in insulation 5 products. Glass fiber compositions that meet the standard in the proposed regulations are considered to be free of suspicion as a disease causing agent and can be used for both commercial and residential installations.

The regulations are based on a desire to minimize the residence time of the glass fiber in the lungs. It is a hope that minimizing the residence time of the glass fiber will 10 decrease the possibility, if any, of subsequent disease.

The proposed German regulations for biosolubility require that glass fibers have a numerical index (KI) greater than or equal to 40 to be considered to be free of suspicion. The KI index, which is sometimes referred to as the Wardenbach Index, is described by the equation: KI = Z (Na20, K20, CaO, MgO, BaO, B203) - 2(A1203) where the values for each oxide correspond to the weight percentage of that oxide in the glass composition.

The index used in the regulation places severe constraints on the compositions of the glass, expressly on the levels of alumina (A1203) and implicitly on the level of silica 2 0 (Si02)in the glass composition. Manufacturers must now produce glass fibers which meet the proposed regulations, while maintaining standard performance criteria for the products. The criteria include that the glass fiber must be producible using standard wool processes, have sufficient durability in use, and acceptable insulating properties.

Silica is the primary component in glass fiber and provides most of the structural 2 5 and physical properties of the fiber. Alumina is primarily used in the fiber to provide additional durability to the fiber.

Initial attempts to produce glass fiber that complies with the regulations involved using reduced levels of alumina in the glass composition to increase the KI index. However, low alumina glass fibers tend to have poor durabilities.

A number of glass composition have been reported as having improved biosolubility or biodegradability. For example, Potter, U.S. Patent No. 5,055,428, Cohen et al., U.S. Patent No. 5,108,957, Nyssen, U.S. Patent No. 5,332,698, and Bauer et al., U.S. Patent No. 5,401,693, all describe glass fibers having improved biosolubility. Also, 2 Printed from Mimosa WO 99/06332 PCT/US98/15701 published PCT applications WO 95/31411, WO 95/32925, WO 95/32926, WO 95/32927, and WO 95/35265 and numerous published German applications have reported glass compositions having increased biodegradability.

Despite the improvements presented in the aforementioned patents and 5 applications, the glasses failed to meet the KI > 40 standard or significant processing and performance problems remain. The decreased performances and increased processing costs for glass compositions designed to meet the new biological standards is a clear shortcoming in the industry. In addition, higher alumina compositions of the prior art provide performance versatility, yet are either not acceptable in the emerging regulated 10 marketplace or suffer from increased processing costs. Accordingly, there is still a need for a glass composition which has increased biosolubilities (KI value > 40), while possessing acceptable processing properties, such as viscosity and liquidus temperatures, as well as acceptable performance and durability in use.

BRIEF SUMMARY OF THE INVENTION 15 The above objectives and others are accomplished by glass compositions in accordance with the present invention. The glass compositions contain at least 2.0 wt % A1203 to give resulting glass fiber an acceptable chemical durability for product performance, but no more than 3.0 wt % to ensure the fiber maintains a relatively high biosolubility. The compositions further include relatively high amount of Na,0 + K20 + 2 0 MgO + CaO, which tends to increase fiber biosolubility and allows for the use of reduced amounts of B203 in the composition.

The glass compositions have KI values that generally equal or exceed a KI value of 40 and are suitable for rotary processing. The compositions have liquidus temperatures below about 1800°F (982°C), and have viscosities above 300 Poise at the liquidus 25 temperatures.

In one aspect of the invention glasses are formulated with relatively high amounts of B2Oj and low amounts of CaO + MgO. The high B2Oj glasses were found to have very lovfr liquidus temperatures (<1650°F [898°C]) and higher viscosities (> 1,000 Poise) at the liquidus temperature.

In another aspect of the invention, glasses are formulated with relatively low amounts of B:03 and high amounts of CaO + MgO. The low B203 glasses were found to have slightly higher liquidus temperatures but still sufficiently low to be formed into 3 Printed from Mimosa WO 99/06332 PCT/US98/15701 fibers by the rotary process (liquidus temperatures < 1800°F (982°C), and viscosities at the liquidus temperature > 300 Poise).

In some situations the low B203/high (CaO + MgO) glasses are highly advantageous. For example, lower amounts of B203 can result in significantly lower 5 batch costs.

Also, the lower B203 level in the composition can result in lower volatile emissions both during melting and forming. When formed by the rotary process, the lower viscosity low B203 glasses can be extruded through the spinner holes and attenuated without significant reheating of the fibers.

In another aspect of the invention, glasses are formulated with low amounts of MgO, generally below about 3.0 to 3.5 wt % have significantly improved chemical durabilities with respect to water. These compositions provide for an improved product performance in addition to improved biosolubility.

In another aspect of the invention, glasses are formulated with higher amounts of MgO, generally between about 2.0 and 6.0 wt %, and preferably between about 3.0 and 5.0 wt %. It was found that these glasses could be formulated with lower amounts of B2Oj, while still maintaining an acceptable liquidus temperature and viscosity at the liquidus temperature. Advantages of these glasses include lower cost and less volatile emissions during melting and forming. 2 0 The compositions of the present invention provides glass compositions that meet proposed biosolubility standards, while maintaining acceptable performance and durability as glass fiber insulation. Accordingly, the present invention overcomes the aforementioned difficulties of the prior art in meeting both public health standards and commercial requirements. These advantages and others will become apparent from the 2 5 following detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described generally with reference to present preferred embodiments of the invention only for the purpose of providing examples of the invention and not for purposes of limiting the same. 3 0 The applicants .have found that acceptable glass processing and fiber biosolubility and durability can be maintained in glass fiber by providing compositions including alumina in a range of 2-3%, B203 in the range of 6-15%, and increased levels of alkali and alkaline Printed from Mimosa preferably from 2.1-2 To compensati WO 99/06332 PCT/US98/15701 oxides over the prior art. Compositions of the present invention provide a balance between increased durability and biosolubility to address the shortcomings of the prior art.

The Si02 consent in compositions of the present invention ranges from 49-54%. The present invention provides for lower levels of silica to provide for increased levels of additives that are used to improve the biosolubility and the durability of the resulting glass fibers.

The A1203 content in the composition should be approximately 2% or higher to provide sufficient performance durability. However, as the alumina content begins to exceed approximately 3%, the biosolubility of the composition will begin to deteriorate. It 10 is preferable that the alumina content of the composition ranges from 2.1 -2.9% and more .6% to provide a more balanced composition. e for the increased levels of alumina and its detrimental affect on the biosolubility, increased levels of alkali and alkaline oxides are included in the composition. Specifically, higher levels of MgO, CaO, Na20 and K20 can be used to improve the KI 15 index and to lower the liquidus temperature of the compositions.

Na20 is included in an amount ranging from approximately 16-22% depending on Na20 will generally provide for lower viscosities and better melting glass. Preferably, the amount of Na20 ranges from 18-21% and more % in the composition. In this range, the amount of B203 in the composition can be reduced as further discussed within.

K20 is included in lower amounts, generally 0-2%, depending upon the amount of composition. K20 at low levels tends to enhance the characteristics For example, somewhat lower liquidus temperatures can be achieved without substantial quantities of B203, if the combined amount of K20 and Na20 is 2 5 approximately 20% o r higher.

MgO is included in the composition ranges from 0-8% to provide for somewhat lower liquidus temperatures and viscosities at a lower cost. When MgO is included in quantities less than approximately 3.5%, the resulting glass fibers have improved durability with respect to water.

In addition, when MgO is included in a range of about 2-6%, and more preferably 3- itions can be formulated with lower B203 quantities. When formed by lower viscosity low B203 glasses can be extruded through the spinner holes and attenuated without significant reheating of the fibers. the desired properties characteristics for the preferably from 19-2 Na20 included in the associated with Na20 In addition, w 5%, the glass compos the rotary process, th Printed from Mimosa WO 99/06332 PCT/US98/15701 CaO is included in the composition in quantities ranging from 7-14%. The CaO provides for a lower viscosity and improved durability.

B203 is included in the composition in quantities ranging from 5.5-15%. The B203 primarily serves to significantly lower the liquidus temperature and the viscosity of the 5 composition, but also provides durability in resulting fibers. The glass compositions formed with high concentration of B203, e.g. 13%, were found to have very low liquidus temperatures (<1650°F [899°C]) and higher viscosities (> 1,000 Poise) at the liquidus temperature.

While including high concentrations of B203 in the glass compositions tends to 10 increase the cost, high B203 glasses can be formed into fibers at quite low temperatures and at high viscosities. These forming conditions can greatly increase the spinner life which can compensate for the increased cost of the glass batch.

Prior art glass compositions conforming to the KI index regulations generally provide for increased levels of B203 to compensate in part for the increased levels of 15 alumina. However, a disadvantage of including increased levels of B203 are higher costs associated with B203. Another disadvantage is that B203 is volatile and higher concentrations produce higher emissions that must be controlled, which can further lead to increased costs. For these reasons, it is preferred to limit the B203 content to 15%.

In view of the disadvantages associated with the various constituents included in 2 0 glass compositions, the present invention attempts to balance the composition to provide for more versatile and better performing glass compositions.

The following examples are provided to demonstrate the present invention and not to limit the same.

Examples A number of compositions were prepared by methods known in the art to provide examples of compositions of the present invention. For each sample, the liquidus temperature of the composition was determined. Also, the temperature at which the viscosity of the glass is approximately 1000 poise was determined. The viscosity at the 30 liquidus temperature (rj^) is shown for a number of compositions.

In addition, durability testing was performed on a number of samples. The durability test consisted of preparing 10 pm diameter continuous fibers from each composition. A 1 g sample of the fiber was placed in 100 ml of water and maintained at a 6 Printed from Mimosa WO 99/06332 PCT/US98/15701 temperature of 96°F (36°C) for 24 hours. Following the water exposure, the sample was removed from the water, dried and weighed. The post-test weight of the sample was compared to the pretest weight to calculate the percent weight loss during testing.

Constituent Sample # 1 2 3 Si02 53.69 53.69 50.72 A1A 2.0 2.0 3.0 BA .0 8.0 11.9 Na20 19.3 19.3 19.3 KjO 0.7 0.7 0.7 MgO 4.35 4.96 3 CaO 9.88 11.27 11.3 Fe203 0.08 0.08 0.08 KIIndex 40.23 40.23 40.20 Liquidus Temperature TL(°F) 1618 1707 1664 Temp. @ r|=1000 Poise 1632 1643 1600 ^(Poise) 1,170 540 % weight loss 4.12 4.11 Constituent Sample # 4 6 7 Si02 53.42 53.42 53.42 53.42 A1A 2.1 2.1 2.1 2.1 BA 13.1 .1 8.1 8.1 Na20 19.3 19.3 19.3 19.3 k2o 0.7 0.7 0.7 0.7 MgO 3.0 3.0 .0 3.0 CaO 8.3 11.3 11.3 13.3 FeA 0.08 0.08 0.08 0.08 KI Index 40.2 40.2 40.2 40.2 Liquidus Temperature TL(°F) 1511 1661 1712 1759 Temp. @ 1^=1000 Poise 1627 1630 1645 1639 ^(Poise) % weight loss 3.73 3.34 4.05 7 Printed from Mimosa Constituent Sample # 8 9 11 Si02 52.22 52.22 52.22 52.22 A1203 2.5 2.5 2.5 2.5 B203 13.9 .9 8.9 .9 NajO 19.3 19.3 19.3 19.3 K20 0.7 0.7 0.7 0.7 MgO 3.0 3.0 3.0 8.0 CaO 8.3 11.3 13.3 11.3 FeA 0.08 0.08 0.08 0.08 KIIndex 40.2 40.2 40.2 40.2 Liquidus Temperature Tl(°F) 1453 1667. 1751 1793 Temp. @ t|=1000 Poise 1620 1619 1626 1661 ri^Poise) % weight loss 3.44 Constituent\Sample # 12 13 14 Si02 53.69 53.69 53.69 53.69 ai2o3 2.0 2.0 2.0 2.0 BA 14.0 13.0 7.5 7.5 Na,0 19.3 19.3 17.3 21.3 KjO 0.7 0.7 0.7 0.7 MgO 3.13 3.43 .73 4.51 CaO 7.10 7.80 13.0 .22 Fe203 0.08 0.08 0.08 0.08 KIIndex 40.23 40.23 40.23 40.23 Liquidus Temperature TL(°F) 1411 1456 1791 1777 Temp. @ ri=1000 Poise 1624 1624 1671 1616 rinXPoise) ,200 12,300 300 % weight loss 3.65 4.24 Constituent Sample # 16 17 18 Si02 53.42 53.42 52.22 A1A 2.1 2.1 2.5 BA 16.1 13.1 13.9 Na20 19.3 19.3 19.3 K20 0.7 0.7 0.7 MgO 0 0 0 CaO 8.3 11.3 11.3 Fe203 0.08 0.08 0.08 KIIndex 40.2 40.2 40.2 Liquidus Temperature TL(°F) 1433 1627 1601 Temp. @ t|=1000 Poise 1620 1613 1608 Tin/Poise) % weight loss 3.73 2.67 8 Printed from Mimosa WO 99/06332 PCT/US98/15701 As can be seen from the examples, compositions of the present invention provide for increased levels of alumina, while remaining within the proposed KI index biosolubility requirements and maintaining acceptable liquidus temperatures (< 1800°F [982°C]) and viscosities. Theoretically acceptable compositions for rotary process glass 5 fiber production appear to be possible with 2.5% alumina and as little as 5.9% B203.

In addition, the present invention provides for decreasing the amount of B203 used in glass compositions. Increased levels of alkaline and alkali oxides are used to partly compensate for the decreased amounts of B203 used in the present invention; thereby resulting in compositions that meet both the KI index regulations and can be processed by 10 standard rotary methods.

The examples demonstrate that compositions within the present invention can be employed in various quantities to tailor specific properties of the compositions. Examples 1-3 show that compositions ranging from 2-3% A1203 and 8-11.9% B203 have acceptable liquidus temperatures and viscosities, when the high levels of alkali and alkaline oxides 15 are used, (MgO + CaO) > 14 and (K20 + Na20) > 20.

Examples 4-7 show the effect of decreasing the amount of B203 and compensating for the decrease by increasing the MgO and/or CaO concentrations. It appears that at lower levels of B203, substituting MgO for B203 may provide for a lower liquidus temperatures than substituting CaO. 2 0 Examples 8-11 show the range of B203 concentrations with 2.5% A1203 that have properties within the theoretically acceptable range for rotary processing. Examples 12-15 show a similar comparison for 2.0% A1203.

Examples 16-18 show that substituting CaO for B203 at higher levels of B203 results in a composition with 2.0% A1203 Example 16 is included as a comparative 2 5 example to demonstrate the unexpectedly increased durability, in addition to an acceptable liquidus temperature and viscosity of the composition of Example 17. The sample composition of Example 18 containing 2.5% A1203 also has an acceptable liquidus temperature and viscosity.

Generally, the compositions having the highest concentration of B203 have the 30 lowest liquidus temperatures (Examples 8,12,13, and 16). However, the higher B203 concentrations used in the present invention are generally less than the B203 concentrations used in the prior art.

Printed from Mimosa WO 99/06332 PCT/US98/15701 Unexpectedly, higher durabilities were achieved for compositions in which MgO and/or CaO were substituted for B203 (Examples 17 and 5, as compared with Examples 16 and 4, respectively). In addition, the highest durability was achieved in the composition of Example 17, which contained only 2.1% of A1203 and had an increased 5 CaO content and correspondingly decreased B203 content compared to Example 16.

Those of ordinary skill in the art will appreciate that a number of modifications and variations that can be made to specific compositions of the present invention without departing from the scope of the present invention. Such modifications and variations are intended to be covered by the foregoing specification and the following claims.

Printed from Mimosa

Claims

WO 99/06332 PCT/US98/15701 WHAT IS CLAIMED IS:

1. A glass fiber composition comprised of the following ingredients in weight percent: Si02 49-54; A1203 2-3; BA 5.5-15; NajO 16-22; K20 0-2; MgO 0-8; and CaO 7-14, wherein said composition has a liquidus temperature < 1800°F, a viscosity at said liquidus temperature > 300 Poise, and satisfies the equation: (BA + Na20 + K20 + MgO + CaO)- 2* A1203 > 40.

2. The composition of claim 1, wherein the B 203 content ranges from 6-15.

3. The composition of claim 1, wherein said ingredients include: Si02 49-54; A1203 2-3; BA 6-12; Na^ 16-22; K20 0-2; MgO 0-8; and, CaO 8-14.

4. The composition of claim 3, wherein said ingredients include: Si02 50-53.5; A1A 2.1-2.9; BA 7-12; Nap 18-21; K20 0-1.5; MgO 0-3.5; and, CaO 9-13. 11 Printed from Mimosa WO 99/06332 PCT/US98/15701

5. The composition of claim 4, wherein said ingredients include: Si02 51-53.5; A1A 2.1-2.6; BA 7-11; Na^ 19-21; k20 0-1.5; MgO 0-3; and, CaO 9-12.

6. The composition of claim 3, wherein said ingredients include: Si02 50-53.5; a1a 2.1-2.9; ba 7-12; Nap 18-21; k2o 0-1.5; MgO 2-6; and, CaO 9-13.

7. The composition of claim 6, wherein said ingredients include: Si02 51-53.5; a1a 2.1-2.6; ba 7-11; Na20 19-21; KjO 0-1.5; MgO 3-6; and CaO 9-12.

8. The composition of claim 7, wherein said B203 ranges from 7-<10 weight percent of the composition.

9. The composition of claim 7, wherein the quantity (Na20 + K20) > 19.0 weight percent of the composition. 12 Printed from Mimosa WO 99/06332 PCT/US98/15701

10. The composition of claim 1, wherein said ingredients include: Si02 49-54; A1A 2-3; BA 10-15; Nap 16-22; K20 0-2; MgO 0-5; and CaO 7-12, wherein said composition has a liquidus temperature < 1650°F (899°C)and a viscosity at said liquidus temperature > 1000 Poise.

11. The composition of claim 10, wherein said ingredients include: Si02 50-53.5; A1203 2.1-2.9; BA 11-14; Na20 18-21; K20 0-1.5; MgO 2-5; and, CaO 7-10.

12. The composition of claim 11, wherein said ingredients include: Si02 51-53.5; A1A 2.1-2.6; BA 11-13.5; Nap 19-21; K20 0-1.5; MgO 3-5; and CaO 7-10.

13. The composition of claim 10, wherein said ingredients include: Si02 50-53.5; A1A 2.1-2.9; Bj03 11-14; Nap 18-21; K20 0-1.5; MgO 0-3.5; and CaO 7-10. 13 Printed from Mimosa WO 99/06332 PCT/US98/15701

14. The composition of claim 13, wherein said ingredients include: Si02 51-53.5; A1203 2.1-2.6; B203 11.0-13.5 Nap 19-21; K20 0-1.5; MgO 0-3; and CaO 7-10.

15. A glass fiber composition comprising in weight percent: Si02 49-54; A1203 2-3; B203 6-15; Na20 16-22; K20 0-2; MgO 0-8; and CaO 7-14, wherein said composition has a liquidus temperature < 1800°F (982°C), a viscosity at said liquidus temperature > 300 Poise, and satisfies the equation: (B203 + NajO + K20 + MgO + CaO)- 2* A1203 > 40.

16. The composition of claim 15, wherein said composition includes: Si02 49-54; A1203 2-3; B203 6-12; Nap 16-22; K20 0-2; MgO 0-8; and, CaO 8-14.

17. The composition of claim 15, wherein said ingredients include: Si02 49-54; A1203 2-3; b203 10-15; Nap 16-22; K20 0-2; MgO 0-5; and CaO 7-12, wherein said composition has a liquidus temperature < 1650°F (899°C) and a viscosity at said liquidus temperature > 1000 Poise. 14 Printed from Mimosa WO 99/06332 PCT/US98/15701

18. A method of preparing glass fiber comprising: providing a composition comprised of, in weight percent: Si02 49-54; ai2o3 2-3; b203 6-15; Na20 16-22; k20 0-2; MgO 0-8; and CaO 7-14, wherein said composition has a liquidus temperature < 1800°F (982°C), a viscosity at said liquidus temperature >300 Poise, and satisfies the equation: (B 203 + Na20 + K20 + MgO + CaO)- 2* A1203 > 40; heating the composition to at least its liquidus temperature to produce a molten composition; and, forming glass fiber from the molten composition.

19. The method of claim 18, wherein said forming includes forming glass fiber by a rotary process.

20. The method of claim 18, wherein said providing includes providing a composition comprised of in weight percent: Si02 49-54; AI2O3 2-3; ba 6-12; NajO 16-22; K20 0-2; MgO 0-8; and, CaO 8-14.

21. The method of claim 18, wherein said providing includes providing a composition comprised of in weight percent: Si02 49-54; A1A 2-3; BA 10-15; NajO 16-22; K20 0-2; MgO 0-5; and CaO 7-12, wherein the composition has a liquidus temperature < 1650°F (899°C) and a viscosity at the liquidus temperature > 1000 Poise. Printed from Mimosa

22. A composition according to claim 1 or claim 15, substantially as herein described with reference the accompanying examples 1 to 15, 17 and 18.

23. A composition according to any one of claims 1 to 17, substantially as herein described with reference to the accompanying examples 1 to 15, 17 and 18.

24. A composition according to any one of claims 1 to 17, substantially as herein described.

25. Method according to claim 18, substantially as herein described with reference to accompanying examples 1 to 15, 17 and 18,

26. Method according to any one of claims 18 to 21, substantially as herein described with reference to the accompanying examples 1 to 15, 17 and 18.

27. Method according to any one of claims 18 to 21, substantially as herein described. intei '.ectual PROPERTY office of n.z. 3 0 APR 2001 HECEIWEG) 16 END